Heat-stable diketopyrrolopyrrole pigment mixtures

ABSTRACT

The present invention relates to a process for the preparation of a mixture comprising at least two structurally different diketopyrrolopyrrole pigments of formula (1) wherein A 1  and A 2  are each independently of the other an aromatic or heteroaromatic radical, by reacting a succinic acid ester with at least one unsubstituted or substituted aromatic or heteroaromatic nitrile, which process comprises carrying out the reaction in the presence of at least one compound of formula (2) wherein A is an aromatic or heteroaromatic radical, R 3  is hydrogen, halogen, methyl, methoxy, —CF 3  or —CN, R 4  is a linear or, from C 3  upwards, optionally branched C 1 -C3 0 alkyl, C 6 -C 10 aryl or C 6 -C2 4 aralkyl radical, X is —S—, —O—, —CR 5 R 5 ′—, —COO—, —CONR 5 —, —SO—, SO 2 —, —SO 2 NR 5 — or —NR 5 — and R 5  and R 5 ′ are each independently of the other hydrogen or a linear or, from C 3  upwards, optionally branched C 1 -C 30 alkyl, C 6 -C 10 aryl or C 6 -C 24 aralkyl radical, to the use of such a mixture in the coloring of organic material and in cosmetics, and also to novel diketopyrrolopyrrole pigment mixtures

The present invention relates to a process for the preparation ofheat-stable, tinctorially strong diketopyrrolopyrrole pigment mixturesand to their use in the colouring of organic material and in cosmetics,and also to novel diketopyrrolopyrrole pigment mixtures.

The known pigments, especially those of relatively small particle size,which are distinguished by a relatively high tinctorial strength, areoften not able fully to meet today's requirements especially in terms offastness properties such as, for example, fastness to migration, tolight, to weathering and to heat, for example in polyolefins. The sameis also true of pigments for colour filter applications, where a highdegree of transparency, or contrast, and good fastness to heat arerequired.

The problem of the present invention was to make available heat-fast andtinctorially strong transparent pigments, especially in the form ofpigment mixtures, which are distinguished by very good dispersibilityand good warping behaviour, for example in partially crystallineplastics, and which can be produced by a simple and economicallyadvantageous preparation process.

It has now been found, surprisingly, that pigment mixtures having theabove advantageous properties can be obtained using the inventiveprocess described hereinbelow.

The present Application accordingly relates to a process for thepreparation of a mixture comprising at least two structurally differentdiketopyrrolopyrrole pigments of formula

wherein

-   A₁ and A₂ are each independently of the other an aromatic or    heteroaromatic radical, by reacting a succinic acid ester with at    least one unsubstituted or substituted aromatic or heteroaromatic    nitrile, which process comprises carrying out the reaction in the    presence of at least one compound of formula

wherein

-   A is an aromatic or heteroaromatic radical,-   R₃ is hydrogen, halogen, methyl, methoxy, —CF₃ or —CN,-   R₄ is a linear or, from C₃ upwards, optionally branched C₁-C₃₀alkyl,    C₆-C₁₀aryl or C₆-C₂₄aralkyl radical,-   X is —S—, —O—, —CR₅R₅′—, —COO—, —CONR₅—, —SO—, SO₂—, —SO₂NR₅— or    —NR₅—, and-   R₅ and R₅′ are each independently of the other hydrogen or a linear    or, from C₃ upwards, optionally branched C₁-C₃₀alkyl, C₈-C₁₀aryl or    C₆-C₂₄aralkyl radical.

The amount of the compound of formula (2) is advantageously from 1 to 10mol %, especially from 2 to 6 mol %, based on the total amount ofnitrile.

A is preferably an aromatic radical such as, for example, a naphthylradical, diphenyl radical or, especially, a phenyl radical.

A₁ is preferably an aromatic radical such as, for example, a naphthylradical, diphenyl radical or, especially, a phenyl radical.

A₂ is preferably an aromatic radical such as, for example, a naphthylradical, diphenyl radical or, especially, a phenyl radical.

The naphthyl radicals in the meanings of A, A₁ and A₂ may beunsubstituted or, each independently of the others, mono- orpoly-substituted by chlorine, bromine, methyl, tert-butyl, methoxy,phenyl, —CF₃, —S-phenyl or by —SO₂-phenyl.

The diphenyl radicals in the meanings of A, A₁ and A₂ may beunsubstituted or, each independently of the others, mono- orpoly-substituted by chlorine, bromine, methyl, tert-butyl, methoxy,phenyl, —CF₃, —S-phenyl or by —SO₂-phenyl.

The phenyl radicals in the meanings of A, A₁ and A₂ may be unsubstitutedor, each independently of the others, mono- or poly-substituted byhalogen, e.g. chlorine or bromine, C₁-C₄alkyl, e.g. methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, orC₁-C₄alkoxy, e.g. methoxy or ethoxy, —CF₃, —CN, phenyl, —O-aryl, e.g.phenoxy, —SO-aryl, e.g. —SO-phenyl, —SO₂-aryl, e.g. —SO₂-phenyl, or byaryl, e.g. —S-phenyl.

The phenyl radicals in the meanings of A₁ and A₂ are preferablyunsubstituted or, each independently of the others, mono- orpoly-substituted by chlorine, bromine, methyl, tert-butyl, methoxy,phenyl, —CF₃, —S-phenyl or by —SO₂-phenyl.

X is preferably —SO—, —O—, —SO₂— or —S—.

X is especially —SO₂— and more especially —S—.

R₃ is preferably hydrogen.

R₄ as linear or, from C₃ upwards, optionally branched C₁-C₃₀alkyl mayalso, if desired, contain ether, amide or ester groups.

The alkyl chain may in that case be interrupted one or more times by—O—, —NH—, —S—, —CO₂—NH—, —CO₂—O—, —SO₂—O— or by —SO₂—NH—.

R₄ is preferably a C₈-C₂₈alkyl radical, especially a linear C₁₂-C₂₄alkylradical, more especially a linear C₁₆-C₂₀alkyl radical, very especiallya linear C₁₈alkyl radical.

A preferred embodiment of the process according to the invention resultsin mixtures comprising at least one diketopyrrolopyrrole pigment offormula

wherein

-   the two substituents R₁ are each independently of the other    hydrogen, chlorine, bromine, C₁-C₄alkyl, methoxy, —CF₃, —CN, phenyl,    —S-aryl or —SO₂-aryl and-   the two substituents R₂ are each independently of the other    hydrogen, chlorine, bromine, methyl, tert-butyl, methoxy, —CF₃ or    —CN,-   and at least one diketopyrrolopyrrole pigment selected from the    group consisting of structurally different diketopyrrolopyrrole    pigments of formulae

wherein

-   R₁ and R₂ are as defined for formula (3),-   R₆ is hydrogen, halogen, C₁-C₄alkyl, methoxy, —CF₃ or —CN,-   R₇ is a linear or, from C₃ upwards, optionally branched C₁-C₃₀alkyl,    C₈-C₁₀aryl or C₆-C₂₄aralkyl radical,-   X is —S—, —O—, —CR₅R₅′—, —COO—, —CONR₅—, —SO—, SO₂, —SO₂NR₅— or    —NR₅—, and-   R₅ and R₅′ are each independently of the other hydrogen or a linear    or, from C₃ upwards, optionally branched C₁-C₃₀alkyl, C₆-C₁₀aryl or    C₆-C₂₄aralkyl radical.

R₆ is preferably hydrogen.

The radical XR₇ is preferably bonded in the para-position.

R₇ as linear or, from C₃ upwards, optionally branched C₁-C₃₀alkyl mayalso, if desired, contain ether, amide or ester groups.

The alkyl chain may in that case be interrupted one or more times by—O—, —NH—, —S—, —CO₂—NH—, —CO₂—O—, —SO₂—O— or by —SO₂—NH—.

R₇ is preferably a C₈-C₂₈alkyl radical, especially a linear C₁₂-C₂₄alkylradical, more especially a linear C₁₆-C₂₀alkyl radical, very especiallya linear C₁₈alkyl radical.

An especially preferred embodiment of the process according to theinvention results in mixtures comprising at least onediketopyrrolopyrrole pigment of formula

wherein

-   the two substituents R₁′ are each independently of the other    hydrogen, chlorine, bromine, methyl, tert-butyl, methoxy, —CF₃,    phenyl, —S-phenyl or —CN, and-   the two substituents R₂ are hydrogen, chlorine, bromine, methyl,    tert-butyl, methoxy, —CF₃ or —CN,-   and at least one diketopyrrolopyrrole pigment selected from the    group consisting of structurally different diketopyrrolopyrrole    pigments of formulae

wherein

-   R₁′ and R₂ are as defined for formula (3a),-   R₆′ is hydrogen, and-   R₇′ is a linear C₁₈-C₂₀alkyl radical.

Diketopyrrolopyrrole pigment mixtures comprising thediketopyrrolopyrrole pigments of formulae (3a) and (4a) are especiallyimportant in the context of the present invention.

Among the diketopyrrolopyrrole pigment mixtures prepared in accordancewith the invention special preference is given to those mixtures whichcomprise the diketopyrrolopyrrole pigments of formulae

The mixtures (A), (B), (C), (D), (E), (F) and (G) are novel and thepresent Application relates also thereto.

The reaction of a succinic acid ester with at least one unsubstituted orsubstituted aromatic or heteroaromatic nitrile and in the presence of atleast one compound of formula (2) is carried out in accordance withgenerally known processes for the preparation of diketopyrrolopyrrolecompounds in an organic solvent in the presence of a base at elevatedtemperature, as described, for example, in U.S. Pat. No. 4,720,305 or inU.S. Pat. No. 4,579,949.

The preparation of the diketopyrrolopyrrole pigment mixtures (A), (B),(C), (D), (E) and (F) according to the invention is generally carriedout analogously to the process described in U.S. Pat. No. 4,720,305 byreacting a mixture consisting of a compound of formula

wherein R₈ is chlorine, methyl, tert-butyl, phenyl or S-phenyl,

-   and a compound of formula

with a succinic acid diester,

-   or by reacting a mixture consisting of two structurally different    compounds of formula (51) and a compound of formula (52) with a    succinic acid diester.

The preparation of the diketopyrrolopyrrole pigment mixture (G)according to the invention is carried out analogously, using, instead ofthe compound of formula (52), the compound of formula

The preparation of the diketopyrrolopyrrole pigment mixtures (A), (B),(C), (D), (E) and (F) according to the invention can, moreover, also becarried out analogously to the process described in WO99/54332.

The overall concentration of nitriles in the organic solvent is usuallyselected in the range from 5 mol/l to 0.5 mol/l.

The molar ratio of base to succinic acid diester is generally in therange from 0.1 to 10 mol of base to 1 mol of succinic acid diester.

The pressure selected is preferably atmospheric pressure.

The reaction temperature is usually in the range from 60 to 140° C.,preferably in the range from 80 to 120° C.

The reaction duration is usually selected in dependence on thetemperature selected. It is generally in the range from 30 minutes to 20hours.

Using customary methods, for example as described in U.S. Pat. No.4,783,540 and U.S. Pat. No. 4,579,949, the reaction product can beworked up by protonation and subsequently isolated.

Organic solvents may be, for example, polar, non-polar, protic oraprotic organic solvents. In detail, examples of solvents that may beused include ethers, e.g. tetrahydrofuran, dioxane or glycol ethers,e.g. ethylene glycol methyl ether, ethylene glycol ethyl ether,diethylene glycol monomethyl ether or diethylene glycol monoethyl ether,or aromatic hydrocarbons, e.g. benzene or alkyl-, alkoxy- orhalo-substituted benzene, e.g. toluene, xylene, anisole orchlorobenzene, dichloro- or trichloro-benzene, N,N′-dimethylacetamide,N-methylpyrrolidone, or aromatic N-heterocyclic compounds, e.g.pyridine, picoline or quinoline, or alcohols such as secondary andtertiary alcohols, e.g. tert-butanol, sec-amyl alcohol or tert-amylalcohol, and also ethylene glycol or propylene glycol. The mentionedsolvents may also be used in the form of mixtures.

As base there may be used, for example, alkali metals, e.g. lithium,sodium or potassium, or hydroxides thereof, e.g. lithium, sodium orpotassium hydroxide, or their alkali metal amides, e.g. lithium, sodiumor potassium amide, or their alkali metal hydrides, e.g. lithium, sodiumor potassium hydride, or their alkali metal alcoholates, especiallyalcohols of C₄-C₁₀alkanes, e.g. calcium, magnesium, lithium, sodium orpotassium tert-butylate, potassium tert-amylate, potassium2-methyl-2-pentylate, potassium 3-methyl-3-pentylate or potassium3-ethyl-3-pentylate.

Succinic acid diesters are symmetrical or asymmetrical diesters,preferably symmetrical diesters. Preference is given to the use ofsuccinic acid dialkyl esters such as succinic acid di(C₁-C₁₂alkyl)esters, preferably succinic acid di(C₁-C₈alkyl) esters and especiallysuccinic acid di(C₁-C₅alkyl) esters, and also succinic acid diaryl andsuccinic acid monoaryl monoalkyl esters, wherein aryl may beunsubstituted or substituted, for example by one or two halogenradicals, C₁-C₆alkyl or by C₁-Calkoxy. Aryl is preferably phenyl.

Special preference is given to succinic acid diesters such as succinicacid dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester,dipentyl ester, diheptyl ester, dioctyl ester, diisopropyl ester,diheptyl ester, di-sec-butyl ester, di-tert-butyl ester, di-tert-amylester, di[1,1-dimethylbutyl] ester, di[1,1,3, 3-tetramethylbutyl] ester,di[1,1-dimethylpentyl] ester, di[1-methyl-1-butyl] ester,di[1,1-dimethylpentyl] ester, di[1-methyl-1-ethyl-butyl] ester,di[1,1-diethylpropyl] ester, diphenyl ester, di[4-methylphenyl] ester,di[2-methylphenyl] ester, di[4-chlorophenyl] ester,di[2,4-dichlorophenyl] ester or monoethyl monophenyl ester.

The above-mentioned succinic acid diesters are known and, in some cases,commercially available compounds.

If desired, rheology-improving compounds may be added to thediketopyrrolopyrrole pigment mixtures prepared in accordance with theinvention and to the diketopyrrolopyrrole pigment mixtures according tothe invention.

A further preferred embodiment of the present invention accordinglyrelates to compositions comprising diketopyrrolopyrrole pigment mixturesprepared in accordance with the invention and/or diketopyrrolopyrrolepigment mixtures according to the invention and rheology-improvingcompounds.

The amount of rheology-improving compounds used relative to the amountof the pigment mixture is generally in the range from 0.1 to 20% byweight, preferably from 0.5 to 10% by weight.

Rheology-improving compounds are known and are, for example,diketopyrrolopyrrole derivatives or compositions comprisingdiketopyrrolopyrrole derivatives, especiallydiketopyrrolopyrrolesulfonic acid salts, as described, for example, inGB-A-2 238 550, U.S. Pat. No. 4,791,204, U.S. Pat. No. 4,914,211,GB-A-430 875, U.S. Pat. No. 5,271,759, U.S. Pat. No. 5,785,750 or U.S.Pat. No. 5,786,487, or amino-substituted diketopyrrolopyrroles, as knownfrom U.S. Pat. No. 5,334,727, U.S. Pat. No. 5,200,528, U.S. Pat. No.5,685,901, U.S. Pat. No. 5,342,955, U.S. Pat. No. 5,424,452 or U.S. Pat.No. 6,066,202, or silane-substituted diketopyrrolopyrroles, as knownfrom U.S. Pat. No. 5,482,547. Rheology-improving compounds are also, forexample, polymers, as known from U.S. Pat. No. 5,145,524, U.S. Pat. No.5,685,901 or U.S. Pat. No. 5,679,148, or chelate complexes, as describedin U.S. Pat. No. 5,685,901, or inorganic compounds used as coatings, asknown, for example, from U.S. Pat. No. 4,880,472, U.S. Pat. No.4,808,230, U.S. Pat. No. 4,889,562, U.S. Pat. No. 5,522,925 or U.S. Pat.No. 5,641,350, or quinacridone derivatives, as known, for example, fromU.S. Pat. No. 5,827,364, or perylene additives, as described in EP-A-1029 899.

The rheology-improving compound can usually be added during or afterpreparation of the diketopyrrolopyrrole pigment mixture.

The diketopyrrolopyrrole pigment mixture is generally brought intocontact with the rheology-improving compounds by customary methods ofmixing.

A preferred embodiment of the present invention relates, moreover, tocompositions comprising a diketopyrrolopyrrole pigment mixtureobtainable by the method according to the invention together withrheology-improving compounds.

If desired, texture improvers can be added to the diketopyrrolopyrrolepigment mixtures according to the invention.

Suitable texture improvers include, for example, fatty acids having atleast 12 carbon atoms, such as, especially, stearic or behenic acid,stearic or behenic acid amide, salts of stearic or behenic acid, such asmagnesium, zinc or aluminium stearate or behenate, and also quarternaryammonium compounds, such as, especially, tri(C₁-C₄)alkylbenzylammoniumsalts, e.g. trimethyl-, triethyl-, tri-n-propyl-, tri-isopropyl-,tri-n-butyl-, tri-sec-butyl- and tri-tert-butyl-benzylammonium salts,and also plasticisers, such as epoxidised soybean oil, waxes, such aspolyethylene wax, resin acids, such as abietic acid, colophony soap,hydrogenated or dimerised colophony, (C₁₂-C₁₈)paraffindisulfonic acid,alkylphenols and alcohols, such as stearyl alcohol. Also suitable arelauryl amine and stearyl amine, as well as aliphatic 1,2-diols, such as1,2-dodecanediol.

Preferred texture improvers are lauryl amine and stearyl amine,aliphatic 1,2-diols, stearic acid and its amides, salts and esters,epoxidised soybean oil, waxes and resin acids.

Such additives may be added in amounts of from 0.05 to 20% by weight,preferably from 1 to 10% by weight, based on the composition accordingto the invention, before, during or after its preparation.

The diketopyrrolopyrrole pigment mixtures prepared in accordance withthe invention and the diketopyrrolopyrrole pigment mixtures according tothe invention can be used in the colouring of organic material,especially low molecular weight or high molecular weight organicmaterial.

A further embodiment of the invention accordingly relates to a method ofcolouring organic material by mixing organic material and a tinctoriallyeffective amount of a diketopyrrolopyrrole pigment mixture prepared inaccordance with the invention or a diketopyrrolopyrrole pigment mixtureaccording to the invention with one another.

If desired, the products obtained in the preparation of thediketopyrrolopyrrole pigment mixtures can be converted into a disperseform. This can be achieved in a manner known per se. Depending upon thecompound and the intended use, it has proved advantageous to use thecolorants as toners or in the form of preparations.

Low molecular weight organic material may be, for example, mineral oil,lubricating grease or wax.

High molecular weight material having a molecular weight (M_(W)) of from10⁴ to 10⁸ g/mol may be, for example, synthetic and/or naturalsubstances, for example natural resins or drying oils, rubber or casein,or modified natural substances, such as chlorinated rubber, oil-modifiedalkyd resins, viscose, or cellulose ethers or esters, such asethylcellulose, cellulose acetate, propionate or butyrate, celluloseacetobutyrate and nitrocellulose, but especially completely syntheticorganic polymers (thermosetting plastics and thermoplastics), as can beobtained by polymerisation, for example by polycondensation orpolyaddition. The class of the polymers includes, for example,polyolefins, such as polyethylene, polypropylene, polyisobutylene, alsosubstituted polyolefins, such as polymerisation products of monomers,such as vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylicacid esters, methacrylic acid esters, fluorinated polymerisationproducts, such as polyfluoroethylene or polytrifluorochloroethylene or atetrafluoroethylene/hexafluoropropylene mixed polymerisation product,and also copolymerisation products of the mentioned monomers. From therange of polyaddition and polycondensation resins there may be used, forexample, condensation products of formaldehyde with phenols, so-calledphenoplasts, and condensation products of formaldehyde and urea orthiourea; also melamine, so-called aminoplasts; also the polyesters usedas surface-coating resins, either saturated, such as alkyd resins, orunsaturated, such as maleic resins; also linear polyesters,polycarbonates, polyphenylene oxides or silicones, and silicone resins.The high molecular weight organic material may also be a partiallycrystalline or amorphous plastics, such as LLDPE (linear low-densitypolyethylene).

“Partially crystalline plastics” are to be understood as meaningplastics that on solidification form small crystalline nuclei oraggregates (for example spherulites or quadrites), including suchmaterials that do this only in the presence of nucleating agents (forexample organic pigments).

Plastics may be thermoplastic high molecular weight organic materialshaving a molecular weight (M_(W)) of from 10⁴ to 10⁸ g/mol, preferablyfrom 10⁵ to 10⁷ g/mol. Where the plastics are partially crystalline,they usually have a degree of crystallinity (X_(c)) of from 10 to 99.9%,especially from 40 to 99%, more especially from 80 to 99%. Preferredpartially crystalline plastics are homopolymers, block or randomcopolymers and terpolymers of ethylene, propylene, butylene, styreneand/or divinylbenzene, especially α-olefins, such as HDPE (high-densitypolyethylene), LDPE (low-density polyethylene), polypropylene andpolystyrene, as well as polyesters, such as polyethylene terephthalate(PET) and thermoplastic ionomers. Especially preferred partiallycrystalline plastics are polyolefins, especially polyethylene ofhigh-density and polypropylene. The partially crystalline plastics mayalso optionally comprise customary amounts of additives, for examplestabilisers, fluorescent whitening agents, fillers and/or lubricants.

The mentioned high molecular weight compounds may be presentindividually or in mixtures as plastic masses, melts or in the form ofspinning solutions. They may also be in the form of their monomers or inthe polymerised state in dissolved form as film formers or binders forsurface-coatings or for printing inks, e.g. boiled linseed oil,nitrocellulose, alkyd resins, melamine resins and urea-formaldehyderesins or acrylic resins.

The present invention relates also to the use of thediketopyrrolopyrrole pigment mixtures prepared in accordance with theinvention or of the diketopyrrolopyrrole pigment mixtures according tothe invention

in the production of inks, for printing inks in printing processes, forflexographic printing, screen printing, the printing of packaging,security colour printing, intaglio printing or offset printing, forpreliminary stages of printing and for printing textiles, for office orhome use or for graphics applications, for example for paper goods, forballpoint pens, felt-tip pens, fibre-tip pens, cardboard, wood,(wood)stains, metal, stamp pads or inks for impact-printing processes(using impact printing ink ribbons),

in the production of surface-coatings, for industrial or commercial use,for textile decoration and industrial labelling, for coil coatings orpowder coatings or for automotive finishes, for high-solids(low-solvent), aqueous or metallic paints or for pigmented formulationsfor water-based paints, for mineral oils, lubricating greases or waxes,

in the production of coloured plastics for coatings, fibres, plates orshaped substrates,

in the production of non-impact-printing material for digital printing,for thermal wax transfer printing, ink-jet printing or for thermaltransfer printing, and also in the production of polymeric colourparticles, toners, dry copy toners, liquid copy toners orelectrophotographic toners.

The present invention relates also to inks comprising high molecularweight organic material and a tinctorially effective amount of thediketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or of the diketopyrrolopyrrole pigment mixture according tothe invention.

Methods of producing inks, especially for ink-jet printing, aregenerally known and are described, for example, in U.S. Pat. No.5,106,412.

The inks can be produced, for example, by blending thediketopyrrolopyrrole pigment mixtures prepared in accordance with theinvention or the diketopyrrolopyrrole pigment mixtures according to theinvention with polymeric dispersants.

Blending of the diketopyrrolopyrrole pigment mixture prepared inaccordance with the invention or of the diketopyrrolopyrrole pigmentmixture according to the invention with the polymeric dispersant ispreferably carried out according to generally known methods of blending,such as stirring or mixing, the use of an intensive mixer (e.g. of thetrade mark Ultra-Turrax®) being especially recommended.

When blending the diketopyrrolopyrrole pigment mixtures prepared inaccordance with the invention or the diketopyrrolopyrrole pigmentmixtures according to the invention with polymeric dispersants it isadvantageous to use an organic solvent, especially a water-miscibleorganic polar, protic or aprotic solvent, e.g. an alcohol or ketone.

The ratio by weight of the diketopyrrolopyrrole pigment mixture preparedin accordance with the invention or of the diketopyrrolopyrrole pigmentmixture according to the invention relative to the ink is advantageouslyselected in the range from 0.0001 to 75% by weight, especially from0.001 to 50% by weight, based on the total weight of the ink.

The present invention accordingly relates also to a method of producinginks, which comprises blending together high molecular weight organicmaterial and a tinctorially effective amount of the diketopyrrolopyrrolepigment mixtures prepared in accordance with the invention or of thediketopyrrolopyrrole pigment mixtures according to the invention.

The present invention relates also to colorants comprising highmolecular weight organic material and a tinctorially effective amount ofa diketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or of a diketopyrrolopyrrole pigment mixture according to theinvention.

The present invention relates also to a method of producing colorants,which comprises blending together a high molecular weight organicmaterial and a tinctorially effective amount of the diketopyrrolopyrrolepigment mixture prepared in accordance with the invention or of thediketopyrrolopyrrole pigment mixture according to the invention.

The present invention relates also to coloured plastics or polymericcolour particles comprising high molecular weight organic material and atinctorially effective amount of the diketopyrrolopyrrole pigmentmixture prepared in accordance with the invention or of thediketopyrrolopyrrole pigment mixture according to the invention.

The present invention relates also to a method of producing colouredplastics or polymeric colour particles, especially of producingmass-coloured plastics, which comprises blending together a highmolecular weight organic material and a tinctorially effective amount ofthe diketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or of the diketopyrrolopyrrole pigment mixture according tothe invention.

Colouring the high molecular weight organic substances with thediketopyrrolopyrrole pigment mixtures prepared in accordance with theinvention or with the diketopyrrolopyrrole pigment mixtures according tothe invention is carried out, for example, by mixing such a colorant,optionally in the form of a masterbatch, into the substrates using rollmills or mixing or grinding apparatuses, as a result of which thecolorant is dissolved in the high molecular weight material or is finelydistributed therein. The high molecular weight organic materialcomprising the admixed colorant is then processed by methods known perse, such as calendering, compression moulding, extrusion,spread-coating, spinning, casting or by injection moulding, whereby thecoloured material acquires its final shape. Admixture of the colorantcan also be effected immediately prior to the actual processing step,for example by continuously feeding a pulverulent colorant according tothe invention and, at the same time, a granulated high molecular weightorganic material, and optionally also additional ingredients such as,for example, additives, directly into the intake zone of an extruder,where mixing takes place immediately before processing. Generally,however, it is preferable to mix the colorant into the high molecularweight organic material beforehand, since more uniform results can beachieved. In order to produce non-rigid mouldings or to reduce theirbrittleness, it is frequently desirable to incorporate so-calledplasticisers into the high molecular weight compounds prior to shaping.There may be used as plasticisers, for example, esters of phosphoricacid, phthalic acid or sebacic add. In the process according to theinvention, the plasticisers can be incorporated into the polymers beforeor after the incorporation of the colorant. It is also possible, inorder to achieve different colour shades, to add to the high molecularweight organic materials, in addition to the pigment mixtures or pigmentcompositions according to the invention, constituents such as white,coloured or black pigments, in any desired amounts.

A further embodiment of the present invention accordingly relates to amethod of producing coloured, especially mass-coloured, plastics,especially partially crystalline plastics, by shaping thediketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or the diketopyrrolopyrrole pigment mixture according to theinvention together with the plastics in an injection-moulding method.

The constituents of the injection-moulding formulation may be premixedbefore being fed into the injection-moulding machine, or they mayalternatively be fed in individually at the same time. It is alsopossible to premix two or more components, and if desired alsoadditives, and then to feed the mixture into the injection-mouldingmachine together with other components, which may be used individuallyor may likewise be premixed.

A particular embodiment of the processes according to the inventionrelates to their being carried out in masterbatches.

In a masterbatch the concentration of the diketopyrrolopyrrole pigmentmixture prepared in accordance with the invention or of thediketopyrrolopyrrole pigment mixture according to the invention ispreferably from 5 to 70% by weight, based on the total weight of thediketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or diketopyrrolopyrrole pigment mixture according to theinvention and the plastics.

For the colouring of surface-coatings and printing inks, the highmolecular weight organic materials and the diketopyrrolopyrrole pigmentmixture prepared in accordance with the invention or thediketopyrrolopyrrole pigment mixture according to the invention arefinely dispersed or dissolved, optionally together with additives, suchas fillers, dyes, pigments, siccatives (drying agents) or plasticisers,in the same organic solvent or solvent mixture. It is also possible touse a procedure in which the individual components are dispersed ordissolved separately or in which a plurality thereof are dispersed ordissolved together, and only then all of the components combined. Theprocessing is effected according to customary methods, for example byspraying, film-coating or one of the many printing methods, thesurface-coating or the printing ink advantageously being cured thermallyor by irradiation, where appropriate after drying beforehand. When thehigh molecular weight material to be coloured is a surface-coating, itmay be a customary surface-coating or a specialist surface-coating, forexample an automotive finish.

Preference is given to the colouring of thermoplastic plastics,especially in the form of fibres, as well as printing inks. Preferredhigh molecular weight organic materials suitable for colouring inaccordance with the invention are very generally polymers having adielectric constant ≧2.5, especially polyesters, polycarbonate (PC),polystyrene (PS), polymethyl methacrylate (PMMA), polyamide,polyethylene, polypropylene, styrene/acrylonitrile (SAN) andacrylonitrile/butadiene/styrene (ABS). Especially preferred arepolyesters, polycarbonate, polystyrene and PMMA. More especiallypreferred are polyesters, polycarbonate and PMMA, especially aromaticpolyesters, which can be obtained by polycondensation of terephthalicacid, for example polyethylene terephthalate (PET) or polybutyleneterephthalate (PBTP).

Special preference is given also to the colouring of low molecularweight organic material, such as mineral oils, lubricating greases andwaxes, using the diketopyrrolopyrrole pigment mixtures prepared inaccordance with the invention or the diketopyrrolopyrrole pigmentmixtures according to the invention.

The present invention relates also to non-impact-printing materialcomprising high molecular weight organic material and a tinctoriallyeffective amount of a diketopyrrolopyrrole pigment mixture prepared inaccordance with the invention or of a diketopyrrolopyrrole pigmentmixture according to the invention.

The present invention relates also to a method of producingnon-impact-printing material, which comprises blending together a highmolecular weight organic material and a tinctorially effective amount ofthe diketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or of the diketopyrrolopyrrole pigment mixture according tothe invention.

The present invention relates also to toners comprising high molecularweight organic material and a tinctorially effective amount of adiketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or of a diketopyrrolopyrrole pigment mixture according to theinvention.

The present invention relates also to methods of producing toners,wherein a high molecular weight organic material and a tinctoriallyeffective amount of the diketopyrrolopyrrole pigment mixture prepared inaccordance with the invention or of the diketopyrrolopyrrole pigmentmixture according to the invention are blended together.

In a particular embodiment of the method according to the invention,toners, paints, inks or coloured plastics are prepared by processingmasterbatches of toners, paints, inks or coloured plastics in roll millsor mixing or grinding apparatuses.

The invention relates also to a method of modifying the spectrum of abeam of visible light by selective absorption of part of the radiationby means of a coloured medium, which comprises using, as the colouredmedium, a pigmented high molecular weight polymeric material accordingto the invention coated onto a transparent substrate.

The present invention accordingly relates also to colour filtersproduced using the high molecular weight polymeric material comprisingat least one diketopyrrolopyrrole pigment mixture prepared in accordancewith the invention or diketopyrrolopyrrole pigment mixture according tothe invention.

The production of colour filters by sequentially applying a red, blueand green pigment to a suitable substrate, e.g. amorphous silicon, isdescribed in GB-A 2 182 165. The colour filters can be coated, forexample, using inks, especially printing inks, which comprise adiketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or a diketopyrrolopyrrole pigment mixture according to theinvention or they can be produced, for example, by mixing adiketopyrrolopyrrole pigment mixture prepared in accordance with theinvention or a diketopyrrolopyrrole pigment mixture according to theinvention with chemically, thermally or photolytically structurable highmolecular weight material. The rest of the production can be carriedout, for example, analogously to EP-A 654 711 by means of application toa substrate, e.g. an LCD, followed by photostructuring and developing. Afurther document in which the production of colour filters is describedis U.S. Pat. No. 5,624,467.

The colour filters according to the invention can be used with excellentresults, especially in terms of transparency, transmittance and heatstability, in liquid crystal displays, plasma displays orelectroluminescent displays, which may be, for example, active (twistednematic) or passive (super-twisted nematic) ferroelectric displays orlight-emitting diodes.

A tinctorially effective amount of the diketopyrrolopyrrole pigmentmixture prepared in accordance with the invention or of thediketopyrrolopyrrole pigment mixture according to the inventiongenerally means, in the present invention, from 0.0001 to 99.99% byweight, preferably from 0.001 to 50% by weight, and especially from 0.01to 50% by weight, based on the total weight of the material to becoloured therewith.

In particular it has been found that the diketopyrrolopyrrole pigmentmixtures prepared in accordance with the invention and thediketopyrrolopyrrole pigment mixtures according to the invention, forexample in thermoplastic or thermosetting plastic materials, fibres,surface-coatings or printing inks, are distinguished by a pure hue, hightinctorial strength, high saturation and very high transparency, goodfastness to migration, to rubbing, to light and to weathering, very goodheat stability and also by good gloss.

The diketopyrrolopyrrole pigment mixtures prepared in accordance withthe invention or the diketopyrrolopyrrole pigment mixtures according tothe invention can also be used in cosmetic preparations or compositions.The amount of diketopyrrolopyrrole pigment mixtures to be used willdepend on the nature of the cosmetic preparations or compositions.Usually, from 0.0001 to 50% by weight, preferably from 0.5 to 25% byweight, based on the total weight of the cosmetic preparations orcompositions, of the diketopyrrolopyrrole pigment mixtures prepared inaccordance with the invention or of the diketopyrrolopyrrole pigmentmixtures according to the invention will be used.

It is also usual to use, in addition to the diketopyrrolopyrrole pigmentmixtures prepared in accordance with the invention or thediketopyrrolopyrrole pigment mixtures according to the invention, otherpigments, goniochromatic pigments and/or dyes which are customarily usedin cosmetic preparations or compositions. Such inorganic or organicpigments and/or dyes are usually used in an amount of from 0 to 25% byweight, preferably from 2 to 15% by weight, based on the total weight ofthe cosmetic preparations or compositions. Examples of such inorganicpigments can include titanium, zirconium or cerium oxides, and alsozinc, iron or chromium oxides or iron(III) blue (ferric blue). Preferredorganic pigments are, for example, the calcium, barium, zirconium oraluminium salts of acid dyes.

If desired, the pigments can also be used in the form ofsurface-modified pigments, for example modified by perfluoroalkylphosphate, methylpolysiloxanes, methyl hydrogen polysiloxanes orchitosan. Suitable modified pigments are, for example, those describedby B. G. Hays in Am. Inkmaker, (June, 1984) 28, (October, 1986) 13 and(November 1990) 28.

In addition, the pigments can also be used in the form of solidsolutions, as are described in U.S. Pat. No. 4,783,540 and U.S. Pat. No.4,810,304.

Those optionally modified pigments are advantageously used in the formof pigment preparations, in which the pigment is already present indispersed form. Suitable preparations are described, for example, in W.Herbst, K. Hunger: Industrielle organische Pigmente, VCHVerdagsgesellschaft 1995, pages 92 ff.

A further embodiment of the present invention accordingly relates tocosmetic preparations or compositions comprising, based on the totalweight,

-   a) from 0.0001 to 20% by weight of at least one diketopyrrolopyrrole    pigment mixture prepared in accordance with the invention or    diketopyrrolopyrrole pigment mixture according to the invention and-   b) from 80 to 99.9999% by weight of a cosmetically suitable carrier    material.

Suitable carrier materials for the cosmetic preparations andcompositions according to the invention are the customary materials usedin such formulations.

The cosmetic preparations and compositions according to the inventionmay be, for example, in the form of sticks, ointments, creams,emulsions, suspensions, dispersions, powders or solutions. Such cosmeticpreparations or compositions are, for example, lipsticks, mascarapreparations, blushers, eye-shadows, foundations, eyeliners, powders ornail varnishes.

When the preparations are in stick form, for example lipsticks,eye-shadows, blushers or foundations, a considerable part of suchpreparations consists of fatty components, which may consist of one ormore waxes, for example ozokerite, lanolin, lanolin alcohol,hydrogenated lanolin, acetylated lanolin, lanolin wax, beeswax,candelilla wax, microcrystalline wax, carnauba wax, cetyl alcohol,stearyl alcohol, cocoa butter, lanolin fatty acids, petrolatum,petroleum jelly, mono-, di- or tri-glycerides or fatty esters thereofthat are solid at 25° C., silicone waxes, such asmethyloctadecane-oxypolysiloxane andpoly(dimethylsiloxy)stearoxysiloxane, stearic acid monoethanolamine,colophane and derivatives thereof, such as glycol abietates and glycerolabietates, hydrogenated oils that are solid at 25° C., sugar glyceridesand oleates, myristates, lanolates, stearates and dihydroxystearates ofcalcium, magnesium, zirconium and aluminium.

The fatty component may also consist of a mixture of at least one waxand at least one oil in which case the following oils, for example, aresuitable: paraffin oil, purcelline oil, perhydrosqualene, sweet almondoil, avocado oil, calophyllum oil, castor oil, sesame oil, jojoba oil,mineral oils having a boiling point of about from 310 to 410° C.,silicone oils, such as dimethylpolysiloxane, linoleyl alcohol, linolenylalcohol, oleyl alcohol, cereal grain oils, such as wheatgerm oil,isopropyl lanolate, isopropyl palmitate, isopropyl myristate, butylmyristate, cetyl myristate, hexadecyl stearate, butyl stearate, decyloleate, acetyl glycerides, octanoates and decanoates of alcohols andpolyalcohols, for example of glycol and glycerol, ricinoleates ofalcohols and polyalcohols, for example of cetyl alcohol, isostearylalcohol, isocetyl lanolate, isopropyl adipate, hexyl laurate and octyldodecanol.

The fatty components in such preparations in stick form may generallyconstitute up to 99.91% by weight of the total weight of thepreparation.

The cosmetic preparations and compositions according to the inventionmay additionally comprise further constituents, such as, for example,glycols, polyethylene glycols, polypropylene glycols, monoalkanolamides,non-coloured polymeric, inorganic or organic fillers, preservatives, UVfilters or other adjuvants and additives customary in cosmetics.

They comprise, for example, a natural or synthetic or partiallysynthetic di- or tri-glyceride, a mineral oil, a silicone oil, a wax, afatty alcohol, a Guerbet alcohol or an ester thereof, a lipophilicfunctional cosmetic active ingredient, including sun-protection filters,or a mixture of such substances.

A lipophilic functional cosmetic active ingredient suitable for skincosmetics, an active ingredient composition or an active ingredientextract is an ingredient or a mixture of ingredients that is approvedfor dermal or topical application.

The following may be mentioned by way of example:

-   -   active ingredients having a cleansing action on the skin surface        and the hair; these include all substances that serve to cleanse        the skin, such as oils, soaps, synthetic detergents and solid        substances;    -   active ingredients having a deodorising and        perspiration-inhibiting action: they include antiperspirants        based on aluminium salts or zinc salts, deodorants comprising        bactericidal or bacteriostatic deodorising substances, for        example triclosan, hexachlorophene, alcohols and cationic        substances, such as, for example, quaternary ammonium salts, and        odour absorbers, for example ®Grillocin (combination of zinc        ricinoleate and various additives) or triethyl citrate        (optionally in combination with an antioxidant, such as, for        example, butyl hydroxytoluene) or ion-exchange resins;    -   active ingredients that offer protection against sunlight (UV        filters): suitable active ingredients are filter substances        (sunscreens) that are able to absorb UV radiation from sunlight        and convert it into heat; depending on the desired action, the        following light-protection agents are preferred:        light-protection agents that selectively absorb high-energy UV        radiation in the range of approximately from 280 to 315 nm which        causes sunburn (UV-B absorbers) and transmit the        longer-wavelength range of, for example, from 315 to 400 nm        (UV-A range), as well as light-protection agents that absorb        only the longer-wavelength radiation of the UV-A range of from        315 to 400 nm (UV-A absorbers);    -   suitable light-protection agents are, for example, organic UV        absorbers from the class of the p-aminobenzoic acid derivatives,        salicylic acid derivatives, benzophenone derivatives,        dibenzoylmethane derivatives, diphenyl acrylate derivatives,        benzofuran derivatives, polymeric UV absorbers comprising one or        more organosilicon radicals, cinnamic acid derivatives, camphor        derivatives, trianilino-s-triazine derivatives,        phenylbenzimidazole-sulfonic acid and salts thereof, menthyl        anthranilates, benzotriazole derivatives, and/or an inorganic        micropigment selected from aluminium oxide- or silicon        dioxide-coated TiO₂, zinc oxide and mica;    -   active ingredients against insects (repellents) are agents that        are intended to prevent insects from touching the skin and        becoming active there; they drive insects away and evaporate        slowly; the most frequently used repellent is diethyl toluamide        (DEET); other common repellents will be found, for example,        in W. Raab and U. Kindl “Pflegekosmetik”, Gustav-Fischer-Verlag        Stuttgart/New York, 1991, page 161;    -   active ingredients for protection against chemical and        mechanical influences: these include all substances that form a        barrier between the skin and external harmful substances, such        as, for example, paraffin oils, silicone oils, vegetable oils,        PCL products and lanolin for protection against aqueous        solutions, film-forming agents, such as sodium alginate,        triethanolamine alginate, polyacrylates, polyvinyl alcohol or        cellulose ethers for protection against the effect of organic        solvents, or substances based on mineral oils, vegetable oils or        silicone oils as “lubricants” for protecting the skin against        severe mechanical stresses;    -   moisturising substances: the following substances, for example,        are used as moisture-controlling agents (moisturisers): sodium        lactate, urea, alcohols, sorbitol, glycerol, propylene glycol,        collagen, elastin and hyaluronic acid;    -   active ingredients having a keratoplastic effect: benzoyl        peroxide, retinoic acid, colloidal sulfur and resorcinol;    -   antimicrobial agents, such as, for example, triclosan or        quaternary ammonium compounds;    -   oily or oil-soluble vitamins or vitamin derivatives suitable for        dermal application: for example vitamin A (retinol in the form        of the free acid or derivatives thereof), panthenol, pantothenic        acid, folic acid, and combinations thereof, vitamin E        (tocopherol), vitamin F; essential fatty acids; or niacinamide        (nicotinic acid amide);    -   vitamin-based placenta extracts: active ingredient compositions        comprising especially vitamins A, C, E, B₂₁, B₁₂, folic acid and        biotin, amino acids and enzymes as well as compounds of the        trace elements magnesium, silicon, phosphorus, calcium,        manganese, iron or copper;    -   skin repair complexes: obtainable from inactivated and        disintegrated cultures of bacteria of the bifidus group;    -   plants and plant extracts: for example arnica, aloe, beard        lichen, ivy, stinging nettle, ginseng, henna, camomile,        marigold, rosemary, sage, horsetail or thyme;    -   animal extracts: for example royal jelly, propolis, proteins or        thymus extracts;    -   cosmetic oils suitable for dermal application: neutral oils of        the Miglyol 812 type, apricot kernel oil, avocado oil, babassu        oil, cottonseed oil, borage oil, thistle oil, groundnut oil,        gamma-oryzanol, rosehip-seed oil, hemp oil, hazelnut oil,        blackcurrant-seed oil, jojoba oil, cherry-stone oil, salmon oil,        linseed oil, cornseed oil, macadamia nut oil, almond oil,        evening primrose oil, mink oil, olive oil, pecan nut oil, peach        kernel oil, pistachio nut oil, rape oil, rice-seed oil, castor        oil, safflower oil, sesame oil, soybean oil, sunflower oil, tea        tree oil, grapeseed oil or wheatgerm oil.

The preparations in stick form are preferably anhydrous but may incertain cases comprise a certain amount of water which, however, ingeneral does not exceed 40% by weight, based on the total weight of thecosmetic preparation.

When the cosmetic preparations and compositions according to theinvention are in the form of semi-solid products, that is to say in theform of ointments or creams, they may likewise be anhydrous or aqueous.Such preparations and compositions are, for example, mascaras,eyeliners, foundations, blushers, eye-shadows, or concealers for circlesaround the eyes.

When such ointments or creams are aqueous, they are especially emulsionsof the water-in-oil type or of the oil-in-water type that comprise,apart from the diketopyrrolopyrrole pigment mixture prepared inaccordance with the invention or the diketopyrrolopyrrole pigmentmixture according to the invention, from 1 to 98.8% by weight of thefatty phase, from 1 to 98.8% by weight of the aqueous phase and from 0.2to 30% by weight of an emulsifier.

Such ointments and creams may also comprise further conventionaladditives, such as, for example, fragrances, antioxidants,preservatives, gel-forming agents, UV filters, colorants, pigments,pearlescent agents, non-coloured polymers as well as inorganic ororganic fillers.

When the preparations are in the form of a powder, they consistsubstantially of a mineral or inorganic or organic filler such as, forexample, talcum, kaolin, starch, polyethylene powder or polyamidepowder, as well as adjuvants such as binders, colorants etc.

Such preparations may likewise comprise various adjuvants conventionallyemployed in cosmetics, such as fragrances, antioxidants, preservativesetc.

When the cosmetic preparations and compositions according to theinvention are nail varnishes, they consist substantially ofnitrocellulose and a natural or synthetic polymer in the form of asolution in a solvent system, it being possible for the solution tocomprise other adjuvants, for example pearlescent agents.

In that embodiment, the coloured polymer is present in an amount ofapproximately from 0.1 to 5% by weight.

The cosmetic preparations and compositions according to the inventionmay also be used for colouring the hair, in which case they are used inthe form of shampoos, creams or gels that are composed of the basesubstances conventionally employed in the cosmetics industry and atleast one diketopyrrolopyrrole pigment mixture prepared in accordancewith the invention or diketopyrrolopyrrole pigment mixture according tothe invention.

The cosmetic preparations and compositions according to the inventionare produced in conventional manner, for example by mixing or stirringthe components together, optionally with heating so that the mixturesmelt.

Suitable formulations for cosmetic preparations or compositions aredescribed, for example, in WO-A-00/33795 on pages 9 to 20. The 17formulation examples given therein are also suitable for thediketopyrrolopyrrole pigment mixtures prepared in accordance with theinvention or the diketopyrrolopyrrole pigment mixtures according to theinvention if the latter are used, in the same concentrations, instead ofthe diketopyrrolopyrrole (DPP) pigments given therein.

The Examples that follow serve to illustrate the invention. Parts areparts by weight and percentages are percentages by weight, unlessotherwise specified. Temperatures are given in degrees Celsius. Therelation between parts by weight and parts by volume is the same as thatbetween grams and cubic centimeters.

EXAMPLE 1

Preparation of octadecyl-thio-benzonitrile in Accordance with theFollowing Reaction Scheme:

The reaction is carried out under an inert atmosphere in a 5-necked 750ml sulfonating flask provided with a thermometer, a mechanical stirrer,a dropping funnel and a reflux condenser. 100.00 g (0.35 mol, 1.0 eq.)of 1-octadecanethiol are dissolved in 200 ml of dimethylacetamide (DMA)at 30° C. and added over 25 minutes to a white suspension of 48.18 g(0.35 mol, 1.0 eq.) of p-chlorobenzonitrile and 67.72 g (0.49 mol, 1.4eq.) of finely ground potassium carbonate in 200 ml ofdimethylacetamide. The reaction mixture is then heated to 135° C. andstirred at that temperature for 4 hours. The temperature is then reducedto 80° C. and the reaction mixture is stirred for 16 hours to completethe reaction. The reaction mixture is then discharged into 1600.0 g ofwater at room temperature. The white crystalline solid that precipitatesout over one hour is filtered off and dried at 70° C. and 200 mbar.There are obtained 122.6 g (90.4% of theory) of the compound of formula

The compound of formula (52) can also be prepared starting from4-mercaptobenzonitrile in analogy to a process published by S. Karisson,A. Hallberg and S. Gronowitz in J. Organomet. Chem. 1992, 430, 1, 53-60or in analogy to a process published by W. H. Roark, B. D. Roth, A.Holmes, B. K. Trivedi, K. A. Kieft, A. D. Essenburg, B. R. Krause and R.L. Stanfield in J. Med. Chem. 1993, 36, 1662-1668 or also in analogy toa process published by D. A. Shirley and W. H. Reedy in J. Amer. Chem.Soc. 1951, 73, 4885-4886.

EXAMPLE 1B

Preparation of 4-octadecyloxybenzonitrile According to the FollowingReaction Scheme:

In a 750 ml sulfonating flask, 30.0 g (0.252 mol) of4-hydroxybenzonitrile, 84.0 g (0.252 mol) of 1-bromooctadecane and 48.7g (0.353 mol) of finely ground potassium carbonate are introduced into200 ml of N-methylpyrrolidone (NMP) under a nitrogen atmosphere andheated at 120° C., with stirring. After being stirred for 15 hours, themixture is cooled to room temperature and poured into 2 liters of water,whereupon a light-beige solid precipitates out, which is filtered offand washed with water. After drying at 60° C. and 150 mbar, there areobtained 90.8 g (97% of theory) of a colourless crystalline solid offormula

EXAMPLE 2

Preparation of a Mixture Comprising the Pigments of Formulae

according to the following reaction scheme:

The reaction is carried out under an inert atmosphere in a 5-necked 750ml sulfonating flask provided with a thermometer, a mechanical stirrer,a dropping funnel and a reflux condenser. The protonation andconditioning step is carried out in a 5-necked 2.5 liter sulfonatingflask provided with a thermometer, a mechanical stirrer and a refluxcondenser.

24.8 g (1.08 mol, 4.0 eq.) of sodium are added to a solution of 400 mlof tert-amyl alcohol and a catalytic amount of Fe(III)Cl₃ at 112° C. Thesodium dissolves, with the formation of sodium tert-amylate and H₂, over40 minutes at 112° C. To the resulting solution there are then added62.0 g (0.53 mol, 1.96 eq.) of p-tolunitrile and 4.2 g (0.01 mol, 0.04eq.) of p-octadecylthiobenzonitrile and then, over 5 hours at 105° C.,92.2 g (0.31 mol, 1.15 eq.) of succinic acid di-tert-amyl ester. Thereaction mixture is stirred for a further 2 hours at 105° C. and cooledto room temperature overnight. The reaction mixture is then added to asolution of 450 ml of water and 450 ml of methanol (at room temperature)over 15 minutes. The resulting mixture is heated to 32° C. and stirredfor 4.5 hours at that temperature. The red precipitate is filtered off,washed with 500 ml of methanol and 500 ml of water and dried at 80° C.and 200 mbar. 75.2 g (about 87% of theory) of a red mixture comprisingthe pigments of formulae (100) and (101) are obtained.

EXAMPLE 2B

A mixture of 24.83 g (1.08 mol) of sodium, a spatula tip of FeCl₃ and400 ml of tert-amyl alcohol is refluxed under a nitrogen atmosphere in a750 ml sulfonating flask. To the resulting clear solution there areadded 59.47 g (0.508 mol) of 4-tolunitrile and 12.56 g (0.0324 mol) of4-octadecylthiobenzonitrile, with stirring. 97.7 ml (0.311 mol) ofsuccinic acid di-tert-amyl ester are then added dropwise over 5 hours.After the addition is complete, the resulting dark-red suspension isstirred for a further 2 hours under reflux and then cooled to roomtemperature. The reaction mixture is then added to a mixture of 450 g ofwater/ice and 450 ml of methanol over a period of 45 minutes, duringwhich the temperature does not rise above 20° C., and is then stirredunder reflux at 83° C. for 4.5 hours to complete the reaction. Thepigment composition obtained in that manner is filtered off and washedwith methanol and water. Drying overnight in vacuo at 80° C. yields 77.7g (82.5% of theory) of a pigment mixture comprising the pigments offormulae (100) and (101), which in PVC results in a transparent redcoloration.

EXAMPLES 2C-2E

Examples 2C-2E are prepared in analogous manner to Example 1A exceptthat the 4-octadecylthiobenzonitrile is replaced by the nitriles set outin the table below.

Coloration Example Nitrile Yield in PVC 2C 4-decylthiobenzonitrile 82%of theory transparent red 2D 4-decyloxybenzonitrile 82% of theorytransparent red 2E 4-octadecyloxybenzonitrile 81% of theory transparentred

EXAMPLE 3

Preparation of a Mixture Comprising the Pigments of Formulae

according to the following reaction scheme:

The reaction is carried out under an inert atmosphere in a 5-necked 1.5liter sulfonating flask provided with a thermometer, a mechanicalstirrer, a dropping funnel and a reflux condenser. The protonation andconditioning step is carried out in a 5-necked 2.5 liter sulfonatingflask provided with a thermometer, a mechanical stirrer and a refluxcondenser.

24.8 g (1.08 mol, 4.0 eq.) of sodium are added to a solution of 170 mlof tert-amyl alcohol and a catalytic amount of Fe(III)Cl₃ at 112° C. Thesodium dissolves, with the formation of sodium tert-amylate and H₂, over40 minutes at 112° C. To the resulting solution there are then added34.46 g (0.22 mol, 0.8 eq.) of p-(tert-butyl)-benzonitrile. Then 44.64 g(0.32 mol, 1.2 eq.) of p-chlorobenzonitrile, 8.4 g (0.02 mol. 0.08 eq.)of p-octadecylthiobenzonitrile and 59.12 g (0.30 mol) of succinic aciddiisopropyl ester are dissolved in 100 ml of tert-amyl alcohol at 60° C.and added over 3.3 hours to the reaction mixture. In the first hour ofaddition the internal temperature is maintained at 105° C. but is thenreduced to 95° C. A further 10.95 g (0.05 mol. 0.2 eq) of succinic aciddiisopropyl ester are added over an hour and the reaction mixture isstirred at 95° C. for a further hour and cooled to room temperatureovernight. The reaction mixture is then introduced into a solution of1062 g of water and 213 g of methanol (at room temperature) over 20minutes. The resulting mixture is heated to 76° C. and stirred at thattemperature for 4 hours. The dark-red precipitate is then filtered off,washed with 5 liters of methanol and 5 liters of water and dried at 80°C. and 200 mbar. 81.5 g (80% of theory) of a mixture comprising thepigments of formulae (102) and (103) are obtained.

EXAMPLE 4

A mixture of 22.94 g (0.998 mol) of sodium and 199.6 g of tert-amylalcohol is refluxed overnight at a temperature from 110 to 115° C. Theresulting clear solution is stirred at 105° C. and to that solutionthere is added, dropwise over 3 hours, a mixture of 66.21 g (0.481 mol)of p-chlorobenzonitrile, 12.01 g (0.031 mol) of p-octadecylbenzonitrileand 64.22 g (0.317 mol) of succinic acid diisopropyl ester dissolved in121.93 g of tert-amyl alcohol; after the addition is complete, thereaction mixture is stirred for 4 hours.

The reaction mixture is then cooled to 23° C. and discharged into amixture of 422 ml of water and 422 ml of methanol at a temperature offrom 25 to 30° C.; it is then heated to 78° C. (reflux) and maintainedat that temperature for 6 hours. After cooling to room temperature, thesuspension formed is filtered off, washed with 1.5 liters of methanoland 2 liters of water and dried at 80° C. in vacuo overnight.

There are obtained 66 g (70% of theory) of a red mixture comprising thepigments of formulae

which imparts a transparent red colour to PVC.

EXAMPLE 4B

The reaction is carried out under an inert atmosphere in a 5-necked 1.5liter sulfonating flask provided with a thermometer, a mechanicalstirrer, a dropping funnel and a reflux condenser. The protonation andconditioning step is carried out in a 5-necked 2.5 liter sulfonatingflask provided with a thermometer, a mechanical stirrer and a refluxcondenser.

22.96 g (1.0 mol) of sodium are added to a solution of 200 g oftert-amyl alcohol and a catalytic amount of Fe(III)Cl₃ at 112° C. Thesodium dissolves, with the formation of sodium tert-amylate and H₂, over60 minutes at 112° C. Then 66.21 g (0.48 mol) of p-chlorobenzonitrile,5.95 g (0.016 mol) of p-octadecylthiobenzonitrile and 48.16 g (0.238mol) of succinic acid diisopropyl ester (SAI) are dissolved in 121 g oftert-amyl alcohol at 90° C. and added over 2 hours to the reactionmixture. In the first hour of addition the internal temperature ismaintained at 112° C. but is then reduced to 85° C. A further 16.06 g(0.08 mol) of SAI are then added over 3 hours and the reaction mixtureis stirred at 85° C. for a further 4 hours and cooled to roomtemperature. The reaction mixture is then transferred into a solution of552 ml of water and 522 ml of methanol at room temperature over 20minutes. The resulting mixture is heated to 50° C. and stirred at thattemperature for 4 hours. The dark-red precipitate is then filtered off,washed with 8 liters each of methanol and water and dried at 80° C. and200 mbar in a drying cabinet. 88.3 g (96% of theory) of a red mixturecomprising the pigments of formulae (103) and (104) are obtained, whichin PVC results in a transparent red coloration.

Example 4C is prepared in analogous manner except thatoctadecyloxy-benzonitrile is added to the sodium tert-amylate directlyand not together with the p-chlorobenzonitrile and SAI.

EXAMPLE 4D

The reaction is carried out under an inert atmosphere in a 5-necked 1.5liter sulfonating flask provided with a thermometer, a mechanicalstirrer, a dropping funnel and a reflux condenser. The protonation andconditioning step is carried out in a 5-necked 2.5 liter sulfonatingflask provided with a thermometer, a mechanical stirrer and a refluxcondenser.

44.5 g (1.9 mol) of sodium are added to a solution of 348 g of tert-amylalcohol and a catalytic amount of Fe(III)Cl₃ at 115° C. The sodiumdissolves, with the formation of sodium tert-amylate and H₂, over 40minutes at 115° C. Then 137.6 g (1.0 mol) of p-chlorobenzonitrile, 12.3g (32 mmol) of p-octadecylthiobenzonitrile and 94.2 g (0.46 mol) ofsuccinic acid diisopropyl ester (SAI) are dissolved in 220 g oftert-amyl alcohol at 60° C. and added over 2 hours to the reactionsolution. In the first hour of addition the internal temperature ismaintained at 115° C. but is then slowly reduced to 85° C. A further31.0 g (0.15 mol) of SAI are then added over 3 hours. Over a further 3hours, 160 g of an azeotropic mixture of isopropanol and tert-amylalcohol are then distilled off under reduced pressure (350 mbar) at 85°C. The reaction mixture is cooled to room temperature and, over 2.5hours, added to a mixture of 349 g of ice, 170 g of methanol and 163 gof 60% sulfuric acid at 0° C. During the addition, there are added afurther 231 g of MeOH and a total of 1440 g of ice in portions. Theresulting mixture is stirred at 0° C. for 5 hours. The dark-redprecipitate is filtered off, washed with 5 liters each of methanol andwater and dried at 80° C. and 200 mbar in a drying cabinet. There areobtained 170 g (88%) of a red mixture comprising the pigments offormulae (103) and (104), which in PVC results in a transparent redcoloration.

Using the appropriately substituted benzonitriles (Examples 4E-4G fromthe table below) instead of 4-octadecylthiobenzonitrile, furtherpigments are synthesised in the mentioned yields in analogous manner.Examples 4H and 4J are prepared in analogous manner except that thesubstituted benzonitrile is introduced into the sodium tert-amylatedirectly and not added together with the 4-chlorobenzonitrile and SAI.

Example R Yield 4E —O—C₁₀H₂₁ 82% 4F —S—C₁₀H₂₁ 87% 4G —O—C₁₈H₃₇ 88% 4H—S(CH₂)₃SO₃Na 90% 4J —(OCH₂)₃OCH₃ 83%

EXAMPLE 5

38.8 g (1.68 mol) of sodium cut into small pieces and a spatula tip ofFeCl₃ are introduced into 375 ml of tert-amyl alcohol in a 1 litersulfonating flask and heated to reflux (bath temperature of 130° C.). Tothe resulting clear solution there is then added a solution of 72.3 g(0.53 mol) of 3-chlorobenzonitrile, 31.0 g (0.23 mol) of4-chlorobenzonitrile, 14.2 g (0.038 mol) of 4-octadecylthiobenzonitrileand also 92.9 ml (0.45 mol) of succinic acid diisopropyl ester (SAI) in225 ml of tert-amyl alcohol via a heated dropping funnel over 3 hours,the bath temperature being set at 95° C. at the beginning. After theaddition is complete, a further 15.5 ml (0.075 mol) of SAI are addedover 30 minutes. The reaction mixture is then cooled to 50° C. andtransferred to a mixture of 375 ml of methanol and 1125 ml of water atroom temperature over 30 minutes. After the addition is complete,stirring is carried out overnight to complete the reaction. The orangesuspension is filtered and washed with methanol and then with water.After drying overnight at 80° C. and 200 mbar in a drying cabinet, thereare obtained 136.9 g (91% of theory) of a pigment which in PVC resultsin a transparent, tinctorially strong, orange coloration.

EXAMPLE 6

25.9 g (1.13 mol) of sodium cut into small pieces and a spatula tip ofFeCl₃ are introduced into 250 ml of tert-amyl alcohol in a 1 litersulfonating flask and heated to reflux (bath temperature of 130° C.).Into the resulting clear solution there is then added a solution of107.2 g (0.50 mol) of 4-phenylthiobenzonitrile, 2.1 g (0.005 mol) of4-octadecylthiobenzonitrile and 73.43 g (0.36 mol) of succinic aciddiisopropyl ester (SAI) in 100 ml of tert-amyl alcohol via a heateddropping funnel (90° C.) over 3 hours. After the addition is complete,stirring is carried out at reflux for a further 1.5 hours. The reactionmixture is then cooled to room temperature and, over 30 minutes,transferred by means of a pump into a mixture of 1000 ml of water/ice,200 ml of methanol and 90 g of glacial acetic acid at 0° C. After theaddition is complete, stirring is carried out overnight at 0-10° C. tocomplete the reaction. The red suspension is then filtered and washedwith methanol and then with water. After drying overnight at 70° C. and200 mbar in a drying cabinet, there are obtained 106.3 g (87% of theory)of a pigment which in PVC results in a transparent, tinctorially strong,red coloration.

EXAMPLE 6B

107.2 g (0.30 mol) of a commercially available form of C.I. Pigment Red254 and 97.4 g (0.71 mol) of anhydrous finely ground potassium carbonateare introduced into 1 liter of N,N-dimethylformamide (DMA) in a 2.5liter sulfonating flask and stirred vigorously under a nitrogenatmosphere at 70° C. A mixture of 65.8 g (0.585 mol) of thiophenol and4.52 g (0.015 mol) of 1-octadecylthiol is then added dropwise via adropping funnel. The mixture is then stirred at 130° C. for 2.5 hoursand subsequently stirred overnight at 110° C. to complete the reaction.After cooling to room temperature, the mixture is slowly added to amixture of 45 g of glacial acetic acid, 2.25 liters of methanol and 450ml of water and, after addition is complete, is stirred for 2 hours. Thered precipitate is filtered off and then washed successively withmethanol and water. After drying overnight at 80° C. and 200 mbar in adrying cabinet, 149.1 g (98.6% of theory) of a red crude pigment ofcoarse particle size are obtained.

Some of that crude pigment is reacted in accordance with followingprocedure in order further to optimise the particle form:

5.0 g (0.22 mol) of sodium cut into small pieces and a spatula tip ofFeCl₃ are introduced into 200 ml of tert-amyl alcohol in a 750 mlsulfonating flask and, under a nitrogen atmosphere, heated to reflux(bath temperature of 130° C.). To the resulting clear solution there arethen added 25.2 g (about 0.05 mol) of the crude pigment in portions,with stirring. After addition is complete, stirring is carried out for afurther 2 hours under reflux. The reaction mixture is then cooled toroom temperature and, over 30 minutes, transferred by means of a pumpinto a mixture of 500 ml of water/ice, 100 ml of methanol and 18 g (0.3mol) of glacial acetic acid at 0° C. After addition is complete,stirring is carried out at 0-10° C. overnight to complete the reaction.The red suspension is then filtered and washed with methanol and thenwith water. After drying overnight at 70° C. and 200 mbar in a dryingcabinet, there are obtained 24.0 g (95.2% of theory) of a pigment whichin PVC results in a transparent, tinctorially strong, red coloration.

Cosmetic Formulation 1: Powder foundation Number Ingredients Amount [%]Phase A 1 Talc 48.20 2 Mica and Methicone 34.00 (Toshiki SericiteOS-61D) 3 Pigment mixture prepared 5.00 according to Example 2 4 Kaolin6.00 5 Zinc Stearate 3.00 6 Methyl Paraben 0.20 7 Propyl Paraben 0.10Phase B 8 Dicaprylyl Maleate 3.00 9 PEG-400 Diisostearate 0.50

Phase A is put into high shear mixer and mixed until colour arecompletely extended. All ingredients of phase B are put together andmixed until phase B is fully homogenous.

Phase B is sprayed to phase A with high mixing.

The united phases are mixed fully homogenous by a high shear mixer.

There is obtained a powder foundation having excellent in-use propertiesand an intense bright red colour of outstanding fastness to light.

Cosmetic Formulation 2: Lipstick Formulation Number Ingredients Amount[%] 1 Castor Oil LISP 15.00 2 Pigment mixture prepared according to 1.40Example 2 3 FD&C Blue 1 B3016 Aluminum Lake 0.25 4 FD&C Yellow 5 B3014Aluminum Lake 0.20 5 TiO₂ pigment 3.00 6 Cosmetic Yellow C33-8073 1.00 7Red Iron Oxide 3080 3.20 8 Castor Oil LISP 31.40 9 White Beeswax 2.00 10Performalene 400 4.00 11 Camauba Wax 2.00 12 Candelilla Wax 5.00 13Caprylic/Capric Triglyceride 8.00 14 Octyl Methoxycinnamate 7.50 15Lanolin Oil 2.00 16 Stearyl Alcohol 2.00 17 Jojoba Oil 6.00 18 SheaButter 2.00 19 Cetyl Palmitate 3.00 20 Propyl Paraben 0.20 21 TocopherylAcetate 0.10 22 Lipstick Fragrance 0.75

Ingredients 8-21 are mixed at a temperature of 75-80° C. until the phaseis uniform.

Ingredients 1-7 are mixed together and grinded in a ball mill or 3-rollmill. Afterwards ingredients 1-7 are added to the mixture of ingredients8-21. The mixture is mixed at a temperature of 75-80° C. Afterwardsingredient 22 is added and the mixture is mixed at a temperature ofabout 70° C.

A lipstick having excellent in-use properties is obtained in thatmanner.

Cosmetic Formulation 3: Nail varnish: Number Ingredients Amount [%] 1sodium selenite 0.01 2 ethyl acetate 20.00 3 isobutyl acetate 26.99 4isopropyl alcohol 2.00 5 Toluene 20.00 6 Nitrocellulose 17.00 7saccharose acetate isobutyrate 8.00 8 dibutyl phthalate 3.80 91,3-butylene glycol 0.20 10 Pigment mixture prepared 1.00 according toExample 2 11 stearylalkonium hectorite 1.00

A red nail varnish having very good in-use properties and outstandinggloss is obtained. After application of the nail varnish, a waitingperiod of three days and removal of the nail varnish, it is found thatthe nail has remained completely unstained.

1. A mixture comprising diketopyrrolopyrrole pigments of formulae


2. A mixture according to claim 1 comprising the diketopyrrolopyrrolepigments of formulae


3. A mixture according to claim 1 comprising the diketopyrrolopyrrolepigments of formulae


4. A mixture according to claim 1 comprising the diketopyrrolopyrrolepigments of formulae


5. A mixture according to claim 1 comprising the diketopyrrolopyrrolepigments of formulae


6. A mixture according to claim 1 comprising diketopyrrolopyrrolepigments of formulae


7. A method of producing coloured plastics or coloured polymericparticles, which comprises incorporating into plastics or polymericparticles a diketopyrrolopyrrole pigment mixture comprising theformulae:


8. A method according to claim 7, wherein the coloured plastics orcoloured polymeric particles are comprised within a colour filter.
 9. Amixture according to claim 1 comprising the diketopyrrolopyrrolepigments of formula